3-(2-Alkoxycarbonyloxy-Phenyl) Acrylic Acid Esters And Their Use As Precursors For The Delivery Of Olfactory Compounds

ABSTRACT

A compound of formula (I), their use as precursors and a method of their production 
     
       
         
         
             
             
         
       
     
     wherein n, Y, R, R 2 , R 3 , and R 4  has the same meaning as given in the specification.

The present invention refers to 3-(2-alkoxycarbonyloxy-phenyl)acrylicacid esters and their use as precursors for the delivery of olfactorycompounds. This invention relates furthermore to a method of theirproduction and to consumer products comprising them.

A principal strategy currently employed in imparting odors to consumerproducts is the admixing of the fragrance directly into the product.There are, however, several drawbacks to this strategy. The fragrancematerial can be too volatile and/or too soluble in water, resulting infragrance loss during manufacturing, storage, and use. Many fragrancematerials are also unstable over time. This again results in loss duringstorage. In many consumer products it is desirable for the fragrance tobe released slowly over time. Microencapsulation and inclusion complexeswith cyclodextrins have been used to help decrease volatility, improvestability and provide slow-release properties. However, these methodsare for a number of reasons often not successful. In addition,cyclodextrins can be too expensive for use in many applications. It istherefore desirable to have a fragrance delivery system which is capableof releasing the fragrant compound or compounds in a controlled manner,maintaining a desired odour or fragrance over a prolonged period oftime.

The principle of using precursors for the delivery of fragrancecompounds appeared for the first time some years ago in the literature.The use of 3-(2-hydroxyaryl)acrylic acid esters (compound A below) isdescribed in EP 0 936 211. This delivery system releases one or moreolfactory compounds upon exposure to light. Using this system in variousconsumer products leads to a prolonged release of the fragrantcompound(s). Unfortunately, the use of 3-(2-hydroxyaryl)acrylic acidesters may lead to discoloration, such as yellow discoloration, not onlyof consumer products, such as laundry care products, e.g. fabricsofteners and detergents, comprising it, but it also may lead todiscoloration of the substrate, for example, the fabric to which theproduct is applied during the washing cycle or rinse cycle.Discoloration of a product such as a fabric in general is not desired,thus there still remains a need for precursors having the advantageousability to release one or more olfactory compounds, but without causingdiscoloration.

It has now been found that certain 3-(2-alkoxycarbonyloxy-phenyl)acrylicacid esters have the ability to release one or more olfactory compoundswithout showing discoloration to be visible to the naked eye.Surprisingly, it has been found that certain phenol protecting groups,in particular esters and carbonates, have the ability of rendering theprior art compounds (A)

color-stable in consumer products comprising them.

Thus, it is believed, without restricting the invention in any way, thatthe free phenolic hydroxyl group of the prior art compounds, asdescribed for example in EP 0 936 211 and WO 03/022978, is responsiblefor the discoloration.

Accordingly, a first aspect of the present invention refers to the useof a compound of formula (I) as precursor for olfactory compounds

wherein the acrylic acid ester double bound is of the E configuration;

n is zero or 1;

Y is —CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁₀ hydrocarbon residue of which preferably atleast one residue R⁵, R⁶ and R⁷ is not hydrogen, and the sum of allcarbon atoms (R⁵+R⁶+R⁷) is not greater than 18, preferably the sum ofall carbon atoms is between 6 and 15; or

Y is —CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independently hydrogen or aC₁-C₁₈ preferably C₁-C₁₀, hydrocarbon residue containing one or moreatoms/groups selected from O, N and C(O), of which preferably at leastone residue R⁵, R⁶ and R⁷ is not hydrogen, and the sum of all carbonatoms (R⁵+R⁶+R⁷) is not greater than 18, preferable the sum of allcarbon atoms is between 6 and 15, for example Y is2-(2-butoxy-ethoxy)-ethyl; or

Y is —CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue, of which preferably atleast one of the residues R⁸, R⁹ and R¹⁰ is not hydrogen, the geometryof the enol double bond is E or Z, and the sum of all carbon atoms(R⁸+R⁹+R¹⁰) is not greater than 18, preferable the sum of all carbonatoms is between 6 and 15; or

Y is —CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue containing one or moreatoms/groups selected from O, N and C(O), of which preferably at leastone of the residues R⁸, R⁹ and R¹⁰ is not hydrogen, the geometry of theenol double bond is E or Z, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰)is not greater than 18, preferable the sum of all carbon atoms isbetween 6 and 15;

R² and R³ are independently hydrogen; C₁-C₆ alkyl, e.g methyl, ethyl,iso-propyl, n-butyl, tert-butyl; C₁-C₆ alkoxy residue, e.g. methoxy,ethoxy; —NO₂; —NH₂; —NHCO₂CH₃; —N(C₁-C₆ alkyl)₂, e.g. dimethylamino,diethylamino; —N(hydroxyalkyl)₂, e.g. di(hydroxyethyl)amino,di(hydroxypropyl)amino; —NHC(O)—(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl),e.g. —NHC(O)-methyl or —NHC(O)-phenyl; or

R² and R³ are attached at the positions C(6,7), C(7,8), or C(8,9), andform together with the carbon atoms to which they are attached adioxolane ring or a dioxane ring;

R⁴ in 2- or 3-position is hydrogen; C₁-C₄ alkyl, e.g. methyl, ethyl,tert-butyl; C₂-C₄ alkenyl, e.g. vinyl, propenyl; C₃-C₆ cycloalkyl, e.g.cyclopropyl, cyclopentyl, cyclohexyl; or —CN; and

if n is zero, R is a C₁-C₂₄, preferably C₁-C₁₈, hydrocarbon residue,e.g. methyl, ethyl or phenyl; or C₁-C₂₄, preferably C₁-C₁₈, hydrocarbonresidue containing one or more heteroatoms selected from N, O and Si; or

if n is 1, R is a C₁-C₂₅, preferably C₁-C₁₈, hydrocarbon residue; aC₁-C₂₅ hydrocarbon residue containing one or more atoms/groups selectedfrom N, O, Si, and C(O); or C₁-C₂₅, preferably C₁-C₁₈, hydrocarbonresidue substituted by an ionic substituent of the formula N(R²⁰)₃ ⁺, inwhich R²⁰ is the residue of an alkyl group with 1 to 18 carbon atoms,preferably 1 to 8 carbon atoms, such as trimethylammonium, ortributylammonium; or R is a monovalent residue of the formula (I)

-   -   wherein    -   X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁶ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue, of        which preferably at least one residue R¹⁴, R¹⁵ and R¹⁶ is not        hydrogen, and the sum of all carbon atoms (R¹⁴+R¹⁵+R¹⁶) is not        greater than 18, preferable the sum of all carbon atoms is        between 6 and 15; or    -   X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁶ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue        containing one or more atoms/groups selected from O, N and C(O),        of which preferably at least one residue R¹⁴, R¹⁵ and R¹⁶ is not        hydrogen, and the sum of all carbon atoms (R¹⁴+R¹⁵+R¹⁶) is not        greater than 18, preferable the sum of all carbon atoms is        between 6 and 15, for example X is 2-(2-butoxy-ethoxy)-ethyl; or    -   X is CR¹⁷=CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue, of        which preferably at least one of the residues R¹⁷, R¹⁸ and R¹⁹        is not hydrogen, the geometry of the enol double bond is E or Z,        and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not greater        than 18, preferable the sum of all carbon atoms is between 6 and        15; or    -   X is —CR¹⁷═CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue        containing one or more atoms/groups selected from O, N and C(O),        of which preferably at least one of the residues R¹⁷, R¹⁸ and        R¹⁹ is not hydrogen, the geometry of the enol double bond is E        or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not        greater than 18, preferable the sum of all carbon atoms is        between 6 and 15;    -   R¹² and R¹³ are independently hydrogen; C₁-C₆ alkyl, e.g methyl,        ethyl, iso-propyl, n-butyl, tert-butyl; C₁-C₆ alkoxy residue,        e.g. methoxy, ethoxy; —NO₂; —NH₂; —NHCO₂CH₃; —N(C₁-C₆ alkyl)₂,        e.g. dimethylamino, diethylamino; N(hydroxyalkyl)₂, e.g.        di(hydroxyethyl)amino, di(hydroxypropyl)amino; —NHC(O)—(C₁-C₈        alkyl); or —NHC(O)—(C₃-C₈ aryl), e.g. —NHC(O)-methyl or        —NHC(O)-phenyl; or    -   R¹² and R¹³ are attached at the positions C(vi,vii),        C(vii,viii), or C(viii,ix), and form together with the carbon        atoms to which they are attached a dioxolane ring or a dioxane        ring;    -   R¹¹ in ii- or iii-position is hydrogen; C₁-C₄ alkyl, e.g.        methyl, ethyl, tert-butyl; C₂-C₄ alkenyl, e.g. vinyl, propenyl;        C₃-C₆ cycloalkyl, e.g. cyclopropyl, cyclopentyl, cyclohexyl; or        —CN.

As used in relation to the compounds of formula (I) “hydrocarbonresidue” unless otherwise indicated refers to alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl alkylcycloalkyl, alkenylcycloalkyl,alkenylcycloalkenyl, aryl, alkylaryl or arylalkyl, and “hydrocarbonresidues containing one or more atoms/groups selected from O, N andC(O),” refers to alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,alkylcycloalkyl, alkenylcycloalkyl, alkenylcycloalkenyl, aryl, alkylarylor arylalkyl wherein one or more carbon atoms are replaced by O, Nand/or C(O).

As used herein by “olfactory compound” is meant a molecule having anodour, preferably a pleasant odour, detectable by a human. As usedherein, the terms “olfactory” and “fragrant” are used interchangeably,and refer to the same compounds.

Compounds of formula (I) are preferred wherein n is 1, and Y is theresidue of a fragrant alcohol HO—CR⁵R⁶R⁷ or the residue of the enol formof a fragrant aldehyde of the formula O═(CH)—CHR⁹R¹⁰, or the residue ofthe enol form of a fragrant ketone of the formula O═(CR⁸)—CHR⁹R¹⁰ and ifR is the monovalent residue of formula (I), X is the residue of afragrant alcohol HO—CR¹⁴R¹⁵R¹⁶ or the residue of the enol form of afragrant aldehyde of the formula O═(CH)—CHR¹⁸R¹⁹ or the residue of theenol form of a fragrant ketone of the formula O═(CR¹⁷)—CHR¹⁸R¹⁹.

Even more preferred are compounds of the present invention wherein n is1, Y is the residue of a fragrant alcohol HO—CR⁵R⁶R⁷ or the residue ofthe enol form of a fragrant aldehyde of the formula O═(CH)—CHR⁹R¹⁰ orthe residue of the enol form of a fragrant ketone of the formulaO═(CR⁸)—CHR⁹R¹⁰, and R is selected from methyl, ethyl, propyl, butyl,pentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl or the residue of afragrant alcohol.

For the purpose of the present invention the term “fragrant alcohol” isdefined herein as any alcohol having a molecular weight between 46 and400, preferably between 100 and 300.

Examples of fragrant alcohols of the formula HO—CR⁵R⁶R⁷ andHO—CR¹⁴R¹⁵R¹⁶ include: amyl alcohol; hexyl alcohol*; 2-hexyl alcohol*;heptyl alcohol*; octyl alcohol*; nonyl alcohol*; decyl alcohol*; undecylalcohol*; lauryl alcohol*; myristic alcohol; 3-methyl-but-2-en-1-ol*;3-methyl-1-pentanol; cis-3-hexenol*; cis-4-hexenol*;3,5,5-trimethyl-hexanol; 3,4,5,6,6-pentamethylheptan-2-ol*;citronellol*; geraniol*; oct-1-en-3-ol; 2,5,7-trimethyl-octan-3-ol;2-cis-3,7-dimethyl-2,6-octadien-1-ol; 6-ethyl-3-methyl-5-octen-1-ol*;3,7-dimethyl-oct-3,6-dienol*; 3,7-dimethyloctanol*;7-methoxy-3,7-dimethyl-octan-2-ol*; cis-6-nonenol*; 5-ethyl-2-nonanol;6,8-dimethyl-2-nonanol*; 2,2,8-trimethyl-7(8)-nonene-3-ol;nona-2,6-dien-1-ol; 4-methyl-3-decen-5-ol*; dec-9-en-1-ol **;benzylalcohol; 2-methyl-undecanol; 10-undecen-1-ol; 1-phenyl-ethanol*;2-phenyl-ethanol*; 2-methyl-3-phenyl-3-propenol; 2-phenyl-propanol*;3-phenyl-propanol*; 4-phenyl-2-butanol; 2-methyl-5-phenyl-pentanol*;2-methyl-4-phenyl-pentanoi*; 3-methyl-5-phenyl-pentanol*;2-(2-methylphenyl)ethanol*; 4-(1-methylethyl)benzene-methanol;4-(4-hydroxyphenyl)-butan-2-one*; 2-phenoxy-ethanol*;4-(1-methylethyl)-2-hydroxy-1-methyl benzene; 2-methoxy-4-methyl-phenol;4-methyl-phenol; anisic alcohol*; p-tolyl alcohol*; cinnamic alcohol*;vanillin*; ethyl vanillin*; eugenol*; isoeugenol*; thymol; anethol*;decahydro-2-naphthalenol; borneol*; cedrenol*; farnesol*; fenchylalcohol*; menthol*; 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol; alphaionol*; tetrahydro ionol*; 2-(11-dimethylethyl)cyclohexanol*;3-(1,1-dimethylethyl)cyclohexanol*; 4-(1,1-dimethylethyl)cyclohexanol*;4-isopropyl-cyclohexanol;6,6-dimethyl-bicyclo[3.3.1]hept-2-ene-2-ethanol;6,6-dimethyl-bicyclo[3.1.1]hept-2-ene-methanol*; p-menth-8-en-3-ol*;3,3,5-trimethyl-cyclohexanol; 2,4,6-trimethyl-3-cyclohexenyl-methanol*;4-(1-methylethyl)cyclohexyl-methanol*;4-(1,1-dimethylethyl)cyclohexanol; 2-(1,1-dimethylethyl)cyclohexanol;2,2,6-trimethyl-alpha-propyl-cyclohexane propanol*; 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol*;3-methyl-5-(2,2,3-trimethylcyclopentyl-3-enyl)pent-4-en-2-ol*;2-ethyl-4-(2,2,3-trimethylcyclopentyl-3-enyl)but-2-en-1-ol*;4-(5,5,6-trimethylbicyclo[2.2.1]hept-2-yl)cyclohexanol*;2-(2-methylpropyl)-4-hydroxy-4-methyl-tetrahydropyran*;2-cyclohexyl-propanol*; 2-(1,1-dimethylethyl)-4-methyl-cyclohexanol*;1-(2-tert-butyl-cyclohexyloxy)-2-butanol*;1-(4-isopropyl-cyclohexyl)ethanol*; 2,6-dimethyl-oct-7-en-2-ol**;2,6-dimethyl-heptan-2-ol**; and 3,7-dimethyl-octa-1,6-dien-3-ol**;

whereby * indicates the preferred alcohols and ** indicate the morepreferred alcohols.

For the purpose of the present invention the term “fragrant aldehyde” isdefined herein as any aldehyde having a molecular weight between 100 and450, preferably between 120 and 300.

Examples of fragrant aldehydes of the formula O═(CH)—CHR⁹R¹⁰ andO═(CH)—CHR¹⁸R¹⁹ include:

2,6,10-trimethylundec-9-enal*;1,2,3,4,5,6,7,8,-octahydro-8,8-dimethyl-2-napthalenecar-boxaldehyde;tridecanal; 2-[4-(1-methylethyl)phenyl]ethanal;2,4-dimethyl-cyclohex-3-ene-1-carboxaldehyde*;4-carboxaldehyde-1,3,5-trimethyl-cyclohex-1-ene*;1-carboxaldehyde-2,4-dimethyl-cyclohex-3-ene*;1-carboxaldehyde-4-(4-hydroxy-4-methylpentyl)cyclohex-3-ene*;3,5,5-trimethyl-hexanal; heptanal*; 2,6-dimethyl-hept-5-enal*;decanal**; dec-9-enal; dec-4-enal; 2-methyldecanal*; undec-10-enal**;undecanal*; dodecanal**; 2-methyl-undecanal**; tridecanal; octanal**;nonanal*; 3,5,5-trimethylhexanal; undec-9-enal**; 2-phenyl-propanal*;4-methyl-phenyl-acetaldehyde*; 3,7-dimethyl-octanal*;dihydroxy-3,7-dimethyl-octanal*; 2,6-dimethyl-oct-5-enal;2-[4-(1-methylethyl)phenyl]ethanal*; 3-(3-isopropyl-phenylbutanal**;2-(3,7-dimethyoct-6-enoxy)ethanal;1-carboxaldehyde-4-(4-methyl-3-pentenyl)cyclohex-3-ene*;2,3,5,5,-tetramethyl-hexanal; longifolic aldehyde;2-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)butanal*;2-methyl-3-(4-tert-butylphenyl)propanal**4-(1,1-dimethyl-ethyl)benzene-propanal*;2-[4-(1-methyl-ethyl)-phenyl]propanal;alpha-methyl-1,3-benzodioxole-5-propanal*; 3,7-dimethyl-oct-6-enal*;2-methyl-3-(4-isopropylphenyl)-propionaldehyde*;4-(4-hydroxy-4-methyl-pentyl)cyclohex-3-en-1-carboxaldehyde**;alpha-methyl-1,3-benzodioxole-5-propanal*;1-carboxaldehyde-4-(1,1-dimethylethyl)-cyclohexane;4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal; and[(3,7-dimethyl-6-octenyl)-oxy]acetaldehyde**;

whereby * indicates the preferred aldehydes and ** indicate the morepreferred aldehydes.

For the purpose of the present invention the term “fragrant ketone” isdefined herein as any ketone having a molecular weight between 100 and450, preferably between 120 and 350.

Examples of fragrant ketones of the formula O═(CR⁸)—CHR⁹R¹⁰ andO═(CR¹⁷)—CHR¹⁸R¹⁹ include:

2-heptyl-cyclopentanone; 2,2,6,10-tetramethyltricyclo-[5.4.0.0(6,10)]undecan-4-one benzylacetone*; carvone*;1,2,3,5,6,7-hexahydro-1,1,2,3,3,-pentamentyl-4H-inden-4-one*; methylheptenone*; dimethyl octenone*; 2-(butan-2-yl)cyclohexanone*;2-hexyl-cyclopent-2-en-1-one*;2-(1-methylethyl)-5-methyl-cyclohexanone*;2-(2-methylethyl)-5-methyl-cyclohexanone*; 3-methyl-cyclopentadecanone;4-tert-pentyl-cyclohexanone*; 3-oxo-2-pentyl-cyclopentane-acetic acidmethyl ester**;1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanone*;and 3-methyl-5-propyl-cyclohex-2-en-1-one*;

whereby * indicates the preferred ketones and ** indicate the morepreferred ketone.

Another embodiment relates to compounds of formula (I) wherein n is 1and R and Y have the same meaning as given above and

-   -   I) R², R³ and R⁴ are H;    -   II) R² and R³ is H, and R⁴ is methyl or —CN at C(2) or C(3), or        phenyl at C(3);    -   III) R² is H, R³ is methyl, ethyl, propyl, or isopropyl at        either C(6) to C(8) or methoxy, ethoxy, propyloxy at either C(6)        to C(8), and R⁴ is H, methyl or —CN at C(2) or C(3), or phenyl        at C(3);    -   IV) R² and R³ is methyl at positions C(6,7), C(6,8), C(6,9),        C(7,8), or C(8,9); or R² and R³ is methoxy at C(7,9), and R⁴ is        H, methyl or —CN at C(2) or C(3), or phenyl at C(3);    -   V) R⁴ is H, methyl or —CN at C(2) or C(3), or phenyl at C(3),        and R² is methyl at C(6) and R³ is isopropyl at C(9), or R² is        isopropyl at C(6) and R³ is methyl at C(9).

Compounds of formula (I) are preferred wherein n is 1, R and Y have thesame meaning as given above, R⁴ is hydrogen or methyl at position C(2)or C(3), and R² and R³ is hydrogen, or R² is hydrogen and R³ is7-methoxy, or R² is hydrogen and R³ is 6-methyl, or R² is hydrogen andR³ is 7-methyl, or R² is hydrogen and R³ is 8-methyl, or R² is hydrogenand R³ is 6-tert-butyl, or R² is 6-tert-butyl and R³ is 8-tert-butyl.

The release of the active substances occurs in two successive steps viahydrolysis, preferably in the presence of enzymes, followed byphotoisomerisation/lactonization, as shown in Scheme 1. Due to the twodifferent consecutive cleavage mechanisms, it is possible to control therelease of an olfactory compound at two different stages of the dryingprocess of a substrate to which compounds of the present invention areapplied. That is, for example, the release of an alcohol of the formulaROH (IV) after spin-drying of a fabric in a first step and the releaseof an alcohol (III), or for Y≡CR⁸═CR⁹R¹⁰ a ketone or aldehyde bytautomerisation, and a coumarin of formula (IIa), when exposed to UVlight, e.g. sunlight during line-drying. In other words, a first boostof fragrance is perceivable when the washing machine is opened and asecond boost of fragrance is perceivable during the line-drying process,if exposed to UV-light.

Accordingly, another aspect of the present invention is a process ofproviding an olfactory compound to a substrate comprising the steps:

-   -   a) cleaving a compound of formula (I) by hydrolysis resulting in        a compound of formula (Ia); followed by    -   b) cleaving the compound of formula (Ia) of step a under        activating conditions in the presence of light resulting in a        coumarin (IIa)

In a preferred embodiment, at least the coumarin (IIa) and one of thealcohols (III, IV) are olfactory compounds. Even more preferred arecompounds according to the present invention capable of releasing twocoumarins (IIa, IIb), herein referred to as Type-II compounds, i.e.compounds of formula (I) wherein n is 1 and R is a monovalent residue ofthe formula (I) as shown in Scheme 2. Thus Type-II compounds of formula(I) can yield under activating conditions up to four different olfactorycompounds.

The activating conditions which lead to the first cleavage step comprisethe presence of relative humidity above 20%, preferably above 30% andpreferably the presence of a hydrolase such as lipase, esterase,protease or cytochrome P450.

The activating conditions which lead to the second cleavage stepcomprise the presence of light having a wavelength range of 200 nm to800 nm, although irradiation with light having in its spectrumwavelengths from 250 nm to 400 nm is preferred. The release of thecoumarin of formula IIa/IIIb and an alcohol YOH/XOH, or forYIX=—CR⁸═CR⁹R¹⁰ a ketone or aldehyde by tautomerisation, occurs, forexample, upon exposure to sunlight penetrating through ordinary windows.Needless to say, it is upon exposure to bright sunlight, especiallyoutdoors, that the release of these compounds will occur faster and to agreater extent than upon exposure to interior light of natural orartificial origin. The cleavage of the compound of formula Ia or Ib canalso be initiated by an appropriate artificial light source, for examplea sun-tanning lamp.

The compounds of formula (I) are virtually odourless and insoluble inwater, i.e. the water solubility is equal to or smaller than 10 ppm.

It has been found that the use of compounds of formula (I) solves thediscoloration problem. In addition, the use of compounds of the presentinvention also results in a very high deposition rate. Especially goodresults are obtainable by using Type-II compounds of the presentinvention. Type-II compounds of the present invention are preferredwherein R⁴═R¹¹, R³═R¹³ and R²═R¹². These molecules deposit on a fabricup to 100% by weight based on the amount added to the rinse cycle.

Most of the compounds of the present invention have never been describedin literature and thus are novel in its own right.

Accordingly the present invention refers in a further aspect to acompound of formula (I)

wherein the acrylic acid ester double bound is of the E configuration;

n is zero or 1;

Y is —CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue of which preferably atleast one residue R⁵, R⁶ and R⁷ is not hydrogen, and the sum of allcarbon atoms (R⁵+R⁶+R⁷) is not greater than 18 and at least 6,preferably the sum of all carbon atoms is between 6 and 15; or

Y is —CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁₀, aliphatic residue containing one or moreatoms/groups selected from O, N and C(O), of which preferably at leastone residue R⁵, R⁶ and R⁷ is not hydrogen, and the sum of all carbonatoms (R⁵+R⁶+R⁷) is not greater than 18, preferable the sum of allcarbon atoms is between 6 and 15, for example Y is2-(2-butoxy-ethoxy)-ethyl; or

Y is —CR═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue, of which preferably atleast one of the residues R⁸, R⁹ and R¹⁰ is not hydrogen, the geometryof the enol double bond is E or Z, and the sum of all carbon atoms(R⁸+R⁹+R¹⁰) is not greater than 18, preferable the sum of all carbonatoms is between 6 and 15; or

Y is —CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈, preferably C₁-C₁, hydrocarbon residue containing one or moreatoms/groups selected from O, N and C(O), of which preferably at leastone of the residues R⁸, R⁹ and R¹⁰ is not hydrogen, the geometry of theenol double bond is E or Z, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰)is not greater than 18, preferable the sum of all carbon atoms isbetween 6 and 15;

R² and R³ are independently hydrogen; C₁-C₆ alkyl, e.g methyl, ethyl,iso-propyl, n-butyl, tert-butyl; C₁-C₆ alkoxy residue, e.g. methoxy,ethoxy; —NO₂; —NH₂; —NHCO₂CH₃; —N(C₁-C₈ alkyl)₂, e.g. dimethylamino,diethylamino; —N(hydroxyalkyl)₂, e.g. di(hydroxyethyl)amino,di(hydroxypropyl)amino; —NHC(O)—(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl),e.g. —NHC(O)-methyl or —NHC(O)-phenyl; or

R² and R³ are attached at the positions C(6,7), C(7,8), or C(8,9), andform together with the carbon atoms to which they are attached adioxolane ring or a dioxane ring;

R⁴ in 2- or 3-position is hydrogen; C₁-C₄ alkyl, e.g. methyl, ethyl,tert-butyl; C₂-C₄ alkenyl, e.g. vinyl, propenyl; C₃-C₆ cycloalkyl, e.g.cyclopropyl, cyclopentyl, cyclohexyl; or —CN; and

if n is zero, R is a C₂-C₂₄, preferably C₂-C₁₈, hydrocarbon residue,e.g. ethyl or phenyl; or C₁-C₂₄, preferably C₁-C₁₈, hydrocarbon residuecontaining one or more heteroatoms selected from N, O and Si; or

if n is 1, R is a C₁-C₂₅, preferably C₁-C₁₈, hydrocarbon residue; aC₁-C₂₅ hydrocarbon residue containing one or more atoms/groups selectedfrom N, O, Si, and C(O); or C₁-C₂₅, preferably C₁-C₁₈, hydrocarbonresidue substituted by an ionic substituent of the formula N(R²⁰)₃ ⁺, inwhich R²⁰ is the residue of an alkyl group with 1 to 18 carbon atoms,preferably 1 to 8 carbon atoms, such as trimethylammonium, ortributylammonium; or R is a monovalent residue of the formula (i)

-   -   wherein    -   X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁶ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue, of        which preferably at least one residue R¹⁴, R¹⁵ and R¹⁶ is not        hydrogen, and the sum of all carbon atoms (R¹⁴+R¹⁵+R¹⁶) is not        greater than 18, preferable the sum of all carbon atoms is        between 6 and 15; or    -   X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁸ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue        containing one or more atoms/groups selected from O, N and C(O),        of which preferably at least one residue R¹⁴, R¹⁵ and    -   R¹⁶ is not hydrogen, and the sum of all carbon atoms        (R¹⁴+R¹⁵+R¹⁶) is not greater than 18, preferable the sum of all        carbon atoms is between 6 and 15, for example X is        2-(2-butoxy-ethoxy)-ethyl; or    -   X is —CR¹⁷=CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue, of        which preferably at least one of the residues R¹⁷, R¹⁸ and R¹⁹        is not hydrogen, the geometry of the enol double bond is E or Z,        and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not greater        than 18, preferable the sum of all carbon atoms is between 6 and        15; or    -   X is —CR¹⁷═CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently        hydrogen or a C₁-C₁₈, preferably C₁-C₁₀, hydrocarbon residue        containing one or more atoms/groups selected from O, N and C(O),        of which preferably at least one of the residues R¹⁷, R¹⁸ and        R¹⁹ is not hydrogen, the geometry of the enol double bond is E        or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not        greater than 18, preferable the sum of all carbon atoms is        between 6 and 15;    -   R¹² and R¹³ are independently hydrogen; C₁-C₆ alkyl, e.g methyl,        ethyl, iso-propyl, n-butyl, tert-butyl; C₁-C₆ alkoxy residue,        e.g. methoxy, ethoxy; —NO₂; —NH₂; —NHCO₂CH₃; —N(C₁-C₆ alkyl)₂,        e.g. dimethylamino, diethylamino; N(hydroxyalkyl)₂, e.g.        di(hydroxyethyl)amino, di(hydroxypropyl)amino; —NHC(O)—(C₁-C₈        alkyl); or —NHC(O)—(C₃-C₈ aryl), e.g. —NHC(O)-methyl or        —NHC(O)-phenyl; or    -   R¹² and R¹³ are attached at the positions C(vi,vii),        C(vii,viii), or C(viii,ix), and form together with the carbon        atoms to which they are attached a dioxolane ring or a dioxane        ring;    -   R¹¹ in ii- or iii-position is hydrogen; C₁-C₄ alkyl, e.g.        methyl, ethyl, tert-butyl; C₂-C₄ alkenyl, e.g. vinyl, propenyl;        C₃-C₆ cycloalkyl, e.g. cyclopropyl, cyclopentyl, cyclohexyl; or        —CN.

As used in relation to the compounds of formula (Ia) “hydrocarbonresidue” unless otherwise indicated refers to aliphatic residues, e.g.alkyl, alkenyl, alkynyl, and alicyclic residues such as cycloalkyl,cycloalkenyl alkylcycloalkyl, alkenylcycloalkyl, alkenylcycloalkenyl,aryl, alkylaryl or aryfalkyl, and “hydrocarbon residues containing oneor more atoms/groups selected from O, N and C(O),” refers to aliphaticresidues, e.g. alkyl, alkenyl, alkynyl, and alicyclic residues such ascycloalkyl, cycloalkenyl alkylcycloalkyl, alkenylcycloalkyl,alkenylcycloalkenyl, aryl, alkylaryl or arylalkyl wherein one or morecarbon atoms are replaced by O, N and/or C(O).

The compounds of formula (I) are advantageously prepared from thecorresponding E-3-(2-Hydroxy-phenyl)acrylic acid esters, which in turncan be prepared for example via the following methods.

In a first step, a corresponding alcohol HO—C(R⁴R⁵R⁶) is transformedinto its Li-, Na- or K-salt, preferably its Na-salt, via proceduresknown to the person skilled in the art, then the corresponding coumarinof formula IIa or IIb is added and the mixture is allowed to react atelevated temperature (20-120° C., preferably 50-100° C.) until completeconversion of the coumarin. Standard acid hydrolysis and workup yieldsthe corresponding E-3-(2-Hydroxy-phenyl)acrylic acid ester, according tothe general procedure described by Ganguly, N. et al; SyntheticCommunications 2001, 31(2), pages 301-309.

Alternatively, salicyl aldehyde is reacted with a dialkoxyphosphorylacetic acid ester of HO—C(R⁴R⁵R⁶), prepared via the Arbuzov reactionbetween the corresponding chloro- or bromoacetic acid esters and aphosphoric acid trialkyl ester, under the conditions of aHorner-reaction known to the person skilled in the art.

The preparation of coumarins of formula IIa or IIb are well known to theperson skilled in the art and is described for example by A. G. Osborneet al., J. Chem. Research (S), 2003, 114-115.

The resulting E-3-(2-hydroxy-phenyl)acrylic acid ester preparedaccording to one of the methods described above is then acylated in asecond step with an activated acid derivative, such as an acid halide oran acid anhydride, or a corresponding chloroformate under standardconditions well known to the person experienced in organic synthesis.

The compounds of formula (I) can be used in any product in which aprolonged and defined release of the abovementioned fragrant compoundsis desired. Therefore, these compounds are especially useful infunctional perfumery, in products which are exposed to (sun) lightduring or after application.

The compounds of formula (I) can act as fragrance precursors infunctional and fine perfumery i.e. in fine fragrances, industrial,institutional, home and personal care products. Industrial,institutional and home cleaning products to which the compound offormula (I) can be added include all kinds of detergents, windowcleaners, hard surface cleaners, all-purpose cleaners and furniturepolishes. Preferably, the products are liquids, e.g. fabric conditionercompositions. A substrate, such as a fabric, treated with a productcomprising a compound of formula (I) will diffuse a fresh and/or cleanodor under cleavage conditions for much longer than when treated with aconventional product. Fabrics or clothes washed with such fabricsoftener will release the coumarins and alcohols, aldehydes or ketoneseven after having been stored for weeks in a dark place, e.g. awardrobe.

The compounds of the formula (I) are also useful for application in allkinds of body care products. Especially interesting products are haircare products, for example shampoos, conditioners and hairsprays, andskin care products such as cosmetic products and especially sunprotection products.

The abovementioned examples are of course only illustrative andnon-limiting. Many other products to which the compounds of formula (I)may be added include soaps, bath and shower gels, deodorants and evenperfumes and colognes.

The compounds of formula (I) can be used alone or in combination withother fragrance ingredients, solvents or adjuvants known to thoseskilled in the art. Such ingredients are described, for example, in“Perfume and Flavor Chemicals”, S. Arctander, Ed., Vol. I & II, AlluredPublishing Corporation, Carol Stream, USA, 2003 and include fragrancecompounds of natural or synthetic origin and essential oils.

The amounts in which the compounds of formula (I) are incorporated inthe various above-mentioned products vary within a wide range. Theamounts depend on the nature of the coumarines and alcohols to bereleased, the nature of the product to which the compounds of formula(I) are added and the desired olfactory effect. The amounts used alsodepend on the co-ingredients in a given composition when the compoundsof formula (I) are used in admixture with perfuming co-ingredients,solvents or adjuvants. Typical concentrations are in the order of 0.01%to 5% by weight of the products.

The following non-limiting examples further illustrate the embodimentsof the invention.

EXAMPLE 1 Preparation of 3-(2-Hydroxy-phenyl)acrylic acid3,7-dimethyl-oct-6-enyl ester

To a suspension of NaH (114 g of a 60%-dispersion in mineral oil, 2.85mol) in toluene (500 ml) is added at room temperature a solution ofcitronellol (468 g, 3.0 mol) in toluene (800 ml) over 50 min viadropping funnel. The temperature is raised to 85° C. (bath) over 60 minand stirring continued for further 45 min. Then a solution of coumarin(219 g, 1.5 mol) in toluene (800 ml) is added over 75 min. After further90 min stirring at 80° C. (inside temperature), the deep orangesuspension is cooled to 55° C. and poured on a mixture of 2.5 kg crushedice and 280 ml 37% aq. HCl-solution. The reaction flask is rinsed twicewith 500 ml toluene. Upon stirring for 10 min the colour of the organiclayer fades to a pale yellow. The organic layer is washed twice withwater, then with brine/water 1:1 and dried over MgSO₄. Afterconcentrating in the rotary evaporator the excess citronellol isdistilled off using a short path apparatus (110-125° C./0.03 mbar, head82° C.) to obtain 240 g of citronellol and 463 g of a brownish residue.The latter is dissolved in 600 ml hexane containing 18 ml acetone andcrystallized at −25° C. After filtration and drying 320 g (71%) ofproduct are obtained as white crystals, m.p. 37-39° C.

IR (film): 3500-3100br, 1673vs, 1633w, 1619w, 1598s, 1450s.

¹H-NMR (400 MHz, CDCl₃): 8.10 (d, J=16, 2H), 7.79 (s, 1H), 7.44 (dd,J=7.6, 1.2, 1H), 7.22-7.18 (m, 1H), 6.69 (d, J=16, 2H), 5.09 (sym. m,1H), 4.28 (sym. m, 24H), 2.00 (sym. m, 2H), 1.80-1.15 (series of m, 5H),1.68 (d, J=0.4, 3H), 1.60 (s, 3H), 0.95 (d, J=6.8, 3H).

¹³C-NMR (100 MHz, CDCl₃): 169.1 (s), 155.9 (s), 141.3 (d), 131.4 (d),131.2 (s), 129.1 (d), 124.5 (d), 121.5 (s), 120.3 (d), 117.8 (d), 116.4(d), 63.4 (t), 36.9 (t), 35.3 (t), 29.4 (d), 25.6 (q), 25.3 (t), 19.3(q), 17.6 (q).

MS (EI 70 eV): 302 (<1, M⁺), 165 (15), 147 (83), 138 (45), 81 (100).

EXAMPLE 2 Preparation of 3-(2-Hydroxy-phenyl)acrylic acid dec-9-enylester

To a suspension of NaH (271 g of a 60%-dispersion in mineral oil, 6.81mol) in toluene (1200 ml) is added at room temperature a solution of9-decen-1-ol (1060 g, 6.81 mol) in toluene (1500 ml) over 75 min viadropping funnel. After 10 min stirring a solution of coumarin (495 g,3.39 mol) in toluene (1800 ml) is added over 75 min. The temperature israised to 85° C. (bath) over 45 min. After further 90 min stirring at80° C. (inside temperature), the deep orange suspension is cooled to 50°C. and poured on a mixture of 4 l 10% aq. H₂SO₄-solution and 2 l ofMTBE. The organic layer is washed with saturated aq. NaHCO₃-solution,followed by water and brine. After concentrating i. RV the excess of9-decen-1-ol is removed by thin film evaporation (130° C., 0.05 mbar) toleave 1064 g of residue which is crystallized from hexane at 5° C. Fromthis, 775 g (75%) of product are obtained as pale yellow crystals, m.p.58° C.

IR (film): 3197br, 1670vs, 1598vs, 1451s.

¹H-NMR (400 MHz, CDCl₃): 8.09 (d, J=16, 2H), 7.64 (s, 1H), 7.45 (d, J=8,1H), 7.23-7.19 (m, 1H), 6.90-6.86 (m, 2H), 6.68 (d, J=16, 1H), 5.84-5.77(sym. m, 1H), 5.01-4.91 (m, 2H), 4.23 (t, J=8, 2H), 2.03 (“q”, J=8, 2H),1.71 (quint, J=8, 8), 1.39-1.29 (m, 1H).

¹³C-NMR (100 MHz, CDCl₃): 169.0 (s), 155.8 (s), 141.1 (d), 139.1 (d),131.4 (d), 129.1 (d), 121.5 (s), 120.3 (d), 117.8 (d), 116.4 (d), 114.0(t), 65.0 (t), 33.7 (t), 29.3 (t), 29.3 (t), 29.1 (t), 29.0 (t), 28.8(t), 28.6 (t), 25.8 (t).

MS (EI 70 eV): 302 (10, M⁺), 164 (8), 178 (100), 118 (37).

EXAMPLE 3 3-{2-[2-(2 Dec.9-enyloxycarbonyl-vinylphenoxycarbonyloxy]phenyl}acrylic acid dec-9-enylester

To a suspension of NaH (14.9 g of a 60% dispersion in mineral oil, 0.31mol; 1.1 equiv., oil washed away with hexane under argon atmosphere) intoluene (93 ml) is added at room temperature the solution of9-decen-1-ol (53.2 g, 0.341 mol, 1.1 equiv.) in toluene (93 ml). Thesolution of coumarin (45.3 g, 0.31 mol, 1.0 equiv.) in toluene (93 ml)is then added within 30 min via dropping funnel. The temperature of theoilbath is raised slowly to 85° C. within 30 min, upon which steadyevolution of hydrogen is observed. During the following 3 h stirring at85° C. a gelatine-like orange mixture is formed which is then cooled toroom temperature. The solution of phosgene in toluene (20%, 100 ml, 0.18mol 0.6 equiv.) is added over 45 min. During the addition, the gelbecomes liquid again and the reaction is cooled with an icebath. Themixture is left stirring for 16 h at room temperature, then the excessphosgene is removed by purging with Argon. The mixture is poured on 200ml 2N aq. HCl and 200 g ice. The phases are separated and the organiclayer is washed three times each with water and water/brine 1:1. Afterdrying the over MgSO₄, the volatiles are removed i. RV and the residuedried at 0.05 mbar/50° C. for 30 min. From this, 107.1 g of product wereobtained as a pale yellow oil which contains the 83% of the titlecompound (=90% yield) besides some mixed carbonates. A sample is furtherpurified via column flash chromatography on SiO₂ eluting withhexane/MTBE 4:1 to isolate analytically pure product as a colourlessoil.

IR (film): 1784m, 1713s, 1638m, 1202vs, 758s.

¹H-NMR (400 MHz, CDCl₃): 7.89 (d, J=16, 2H), 7.67 (dd, J=7.6, 1.2, 2H),7.46-7.30 (m, 6H), 6.53 (d, J=16, 2H), 5.08 (sym. m, 2H), 4.26 (sym. m,4H), 1.99 (sym. m, 4H), 1.80-1.15 (4 series of m, 10H), 1.67 (s, 6H),1.59 (s, 6H), 0.95 (d, J=6.4, 6H).

¹³C-NMR (100 MHz, CDCl₃): 166.5 (s), 151.3 (s), 149.2 (s), 137.3 (d),131.3 (s), 131.2 (d), 128.1 (d), 127.0 (s), 126.9 (d), 124.5 (d), 122.3(d), 121.3 (d), 63.3 (t), 37.0 (t), 35.5 (t), 29.6 (d), 25.7 (q), 25.4(t), 19.4 (q), 17.6 (q).

MS (EI 70 eV): 631 (5, M⁺), 493 (10), 475 (100), 431 (26), 337 (65).

EXAMPLE 4 3-(2 Dec. 9-enyloxycarbonyloxy-phenyl)acrylic acid dec-9-enylester a) 3-(2-Chlorocarbonyloxy-phenyl)acrylic acid dec-9-enyl ester

The solution of 3-(2-Hydroxy-phenyl)-acrylic acid dec-9-enyl ester(prepared in Example 2, 47.1 g, 156 mmol) in toluene (550 ml) is cooledwith an ice bath, then phosgene is introduced via dropping funnel (100ml of a 20% solution, 188 mmol, 1.2 equiv), followed byN,N-diethylanilin (27.5 ml, 169 mmol). The resulting turbid solution isstirred at room temperature for 16 h, after which the excess phosgene isremoved by extensive purging with argon. The white suspension is pouredon a mixture of 2 N aq. HCl-solution and ice, the phases are separatedand the aqueous layer is extracted further with toluene. The organiclayers are washed with 2 N aq. HCl-solution, then 3 times with brine andcombined. After drying over MgSO₄, the solvent is removed and theresidue dried at 0.05 mbar/50° C. for 20 min. From this 57.2 g (100%) ofproduct are obtained as a pale yellow oil which is not further purified.

IR (film): 1786s, 1714s, 1639m, 1171s, 1108vs.

¹H-NMR (400 MHz, CDCl₃): 7.77 (d, J=16, 1H), 7.66 (d, J=8, 1H), 7.44 (m,1H), 7.35 (t, J=7, 1H), 7.27 (d, J=8, 1H), 6.50 (d, J=16, 1H), 5.81 (m,1H), 4.99 (dd, J=17, 1, 1H), 4.93 (dd, J=10, 1, 1H), 4.22 (t, J=7, 2H),2.04 (q, J=7, 2H), 1.71 (qd, J=7, 7,2H), 1.36 (br. m, 10H).

¹³C-NMR (100 MHz, CDCl₃): 166.2 (s), 149.6 (s), 149.2 (s), 139.0 (d),136.4 (d), 131.2 (d), 128.1 (d), 127.6 (d), 126.6 (s), 121.8 (d), 121.8(d), 114.1 (t), 64.9 (t), 33.7 (t), 29.3 (t), 29.1 (t), 28.9 (t), 28.8(t), 28.6 (t), 25.8 (t).

MS (EI 70 eV). 344 (4, M⁺), 227 (6), 209 (50), 181 (15), 147 (100), 118(29).

b) 3-(2 Dec. 9-enyloxycarbonyloxy-phenyl)acrylic acid dec-9-enyl ester

The chloroformate prepared above (3.65 g, 10 mmol) in toluene (10 ml) isadded dropwise to the solution of 9-decen-1-ol (1.56 g, 10 mmol) andpyridine (2.0 ml, 25 mmol) in toluene (20 ml) with external ice cooling.The resulting white suspension is warmed to room temperature and stirredfor 4 h, then 2 N aq. HCl-solution (20 ml) is added and stirringcontinued for 5 min. The mixture is then transferred into a separatoryfunnel, the phases are separated and the aqueous phase is furtherextracted with MTBE. The organic layers are washed with brine/H₂O 1:1and dried over MgSO₄. Removal of the solvents and drying at 0.05 mbar(at room temperature) yields a crude which is purified via flashchromatography on SiO₂ eluting with MTBE/hexane 4:1. From this, 3.89 g(80%) of product are obtained as a colourless viscous oil.

IR (film): 2926m, 1764s, 1715s, 1639w, 1212vs.

¹H-NMR (400 MHz, CDCl₃): 7.82 (d, J=16, 1H), 7.62 (dd, J=7.6/1.2, 1H),7.40 (br. t, J=8, 1H), 7.29-7.20 (m, 2H), 6.48 (d, J=16, 1H), 5.85-5.78(m, 2H), 5.02-4.92 (m, 4H), 4.26 (t, 6.8, 2H), 4.19 (t, J=6.8, 2H),2.07-2.02 (m, 4H), 1.80-1.68 (m, 4H), 1.38-1.32 (m, 20H).

¹³C-NMR (100 MHz, CDCl₃): 166.6 (s), 153.2 (s), 149.4 (s), 139.0 (d),139.0 (d), 137.6 (d), 130.9 (d), 127.7 (d), 127.03 (s), 126.3 (d), 122.5(d), 120.6 (d), 114.0 (t), 114.0 (t), 69.2 (t), 64.6 (t), 33.6 (2 t),29.2 (t), 29.2 (t), 29.1 (t), 29.0 (t), 29.8 (t), 28.9 (t), 28.8 (t),28.6 (t), 28.4 (t), 25.8 (t), 25.5 (t).

MS (EI 70 eV) 484 (3, M⁺), 328 (3), 302 (3), 164 (14), 146 (100), 118(20).

EXAMPLE 5 3-[2-(3,7-Dimethyl-oct-6-enyloxycarbonyloxy)phenyl]acrylicacid 3,7-dimethyl-oct-6-enyl ester

The solution of 3-(2-Hydroxy-phenyl)acrylic acid 3,7-dimethyl-oct-6-enylester (6.04 g 20 mmol, as prepared in Example 1) and pyridine (4.0 ml,50 mmol) in toluene (40 ml) is cooled with an icebath and the solutionof citronellyl chloroformate (5.06 g, 22 mmol) in toluene (20 ml) isadded dropwise via dropping funnel over 20 min. The resulting suspensionis stirred at room temperature during 3 days, then quenched by additionof 2 N aq. HCl-solution at 2-3° C. Extraction, separation of phases,washing of the organic layer with brine and drying over MgSO₄, followedby removal of the solvents and drying of the residue under high vacuumyielded 9.7 g (100%) of analytically pure product as a pale yellow oil.

IR (film):1765m, 1715m, 1638w, 1213vs.

¹H-NMR (400 MHz, CDCl₃): 7.81 (d, J=16, 1H), 7.62 (dd, J=1.2 and 7.6,1H), 7.29-7.20 (m, 2H), 6.47 (d, J=16, 1H), 5.10 (sym. m, 2H), 4.32-4.22(m, 4H), 2.00 (sym. m, 4H), 1.85-1.15 (series of m, 10H), 1.68 (“s”,6H), 1.59 (s, 6H), 0.96 (d, J=6, 3H), 0.94 (d, J=6, 3H).

¹³C-NMR (100 MHz, CDCl₃): 166.5 (s), 153.2 (s), 149.4 (s), 137.6 (d),131.3 (s), 131.2 (s), 130.9 (d), 127.8 (d), 127.0 (s), 126.3 (d), 124.4(d), 124.3 (d), 122.5 (d), 120.6 (d), 67.7 (t), 63.1 (t), 36.9 (t), 36.8(t), 35.4 (t), 35.2 (t), 29.5 (d), 29.2 (d), 25.6 (q), 25.3 (t), 25.2(t), 19.3 (q), 19.2 (q), 17.5 (q).

MS (APCI with NH₄OAc, pos.): 502 ([M+NH₄]⁺), 485 (12, M⁺).

EXAMPLE 6 3-(2-Hex-3-enyloxycarbonyloxy-phenyl)acrylic acid3,7-dimethyl-oct-6-enyl ester

Repeating the procedure of Example 5 with 3-(2-Hydroxy-phenyl)acrylicacid 3,7-dimethyl-oct-6-enyl ester (6.04 g 20 mmol), pyridine (4.0 ml,50 mmol) and cis-3-hexenyl chloroformate (3.58 g, 22 mmol) yields 8.60 g(100%) analytically pure product as a pale yellow oil.

IR (film): 1765m, 1715m, 1638w, 1212vs.

¹H-NMR (400 MHz, CDCl₃): 7.81 (d, J=16, 1H), 7.62 (dd, J=1.2 and 7.6,1H), 7.39 (sym. m, 1H), 7.29-7.20 (m, 2), 6.47 (d, J=16, 1H), 5.56 (sym.m, 1H), 5.36 (sym. m, 1H), 5.10 (sym. m, 1H), 4.27-4.23 (m, 4H), 2.52(q, J=8, 4H), 2.11-1.90 (m, 4H), 1.80-1.15 (series of m, 5H), 1.68 (s,3H), 1.61 (s, 3H), 0.97 (t, J=8, 3H), 0.95 (d, J=8, 3H).

¹³C-NMR (100 MHz, CDCl₃): 166.5 (s), 153.2 (s), 149.4 (s), 137.5 (d),135.2 (d), 131.2 (s), 130.9 (d), 127.8 (d), 127.0 (s), 126.3 (d), 124.4(d), 122.5 (d), 122.5 (d), 120.6 (d), 68.4 (t), 63.1 (t), 36.9 (t), 35.4(t), 29.5 (d), 26.5 (t), 25.6 (q), 25.3 (t), 19.3 (q), 17.5 (q), 14.0(q).

MS (APCI with NH₄OAc, pos.): 446 ([M+NH₄]⁺), 429 (11, M⁺).

EXAMPLE 7 3-(2-Acetoxy-phenyl)acrylic acid dec-9-enyl ester

3-(2-Hydroxy-phenyl)acrylic acid dec-9-enyl ester (6.07 g, 20 mmol, asprepared in Example 2) in toluene (40 ml) are added to a suspension ofNaH (840 mg of a 60% dispersion in mineral oil, 20 mmol, 1 equiv.) intoluene (60 ml). The yellow suspension is stirred for 30 min. at RT,then acetyl chloride (1.96 g, 25 mmol, 1.25 equiv.) are added. Theresulting colourless solution is stirred for another 60 min. at RT, thenpoured on H₂O (100 ml). The organic layer is separated, and the aqueouslayer extracted with MTBE. The organic layers are washed with 1 N aq.NaHCO₃-solution, then water and brine. After drying over MgSO₄, thesolvents are removed to yield 6.85 g (99%) of product as a colourlessoil.

IR (film): 1770m, 1713s, 1638w, 1170vs.

¹H NMR (400 MHz, CDCl₃): 8 ppm 1.34 (m, 9H), 1.68 (qd, J=7, 7, 2H), 2.03(q, J=7, 2H), 2.34 (s, 3H), 4.18 (t, J=7, 2H), 4.93 (m, 2H), 5.80 (m,1H), 6.45 (d, J=16, 1H), 7.10 (m, 1H), 7.22 (t, J=7.58, 1H), 7.36 (m,1H), 7.62 (dd, J=8, 2, 1H), 7.75 (d, J=16, 1H).

MS (EI 70 eV): 344 (3, M⁺), 302 (18), 285 (10), 164 (12), 146 (100), 136(11), 118 (30).

EXAMPLE 8 3-(2-Hydroxy-phenyl)-acrylic acid phenethyl ester

The compound is prepared by reaction of coumarin with phenylethanol inthe presence of sodium hydride following the procedure described inExample 2. The title compound is isolated as a white solid, m.p. 40° C.

IR (film): 3261 vs, 1771m, 1738s, 1679vs, 1631vs, 1599 vs, 1174 vs, 752vs, 700 vs.

¹³C-NMR (CDCl₃, 100 MHz): 168.6 (s), 155.8 (s), 141.3 (d), 137.7 (d),131.5 (d), 129.1 (d), 128.9 (d), 128.5 (d), 126.5 (d), 121.5 (s), 120.4(d), 117.7 (d), 116.4 (d), 65.2 (t), 35.1 (t).

¹H-NMR (CDCl₃, 400 MHz): 8.07 (d, J=16, 1H), 7.49 (s, 1H), 7.42 (dd,J=8, 2, 1H), 7.27-7.32 (m, 2H), 7.17-7.26 (m, 5H), 6.86 (td, J=8, 1.1,2H), 6.64 (d, J=16, 1H), 4.43 (t, J=7, 2H), 3.01 (t, J=7, 2H).

MS (EI, 70 eV): 268 (<1, M⁺), 266 (1), 250 (4), 164 (46), 146 (69), 118(60), 104 (79), 91 (100).

EXAMPLE 9 3-(2-Phenethyloxycarbonyloxy-phenyl)-acrylic acid phenethylester

A solution of 3-(2-Hydroxy-phenyl)-acrylic acid phenethyl ester (1.61 g,6.0 mmol) in toluene (15 ml) is added dropwise at room temperature to asuspension formed from chloroformic acid phenethyl ester (1.22 g, 6.6mmol, 1.1 equiv.) and pyridine (0.97 ml, 12.0 mmol, 2.0 equiv.) intoluene (10 ml). The mixture is further stirred at room temperature for16 h, then worked up following the genera procedure described forExample 5 and purified by flash chromatography on SiO₂, eluting withhexane/MTBE 4:1. The title compound (1.61 g, 64% yield) is obtained as acolourless, viscous oil.

IR (film): 1760s, 1710 s, 1212 vs, 1168 vs, 697 vs.

¹H-NMR (CDCl₃, 400 MHz): 7.82 (d, J=16.2 Hz, 1H), 7.60 (dd, J=7.8, 1.6Hz, 1H), 7.36-7.43 (m, 1H), 7.20-7.35 (m, 11H), 7.16 (dd, J=8.2, 1.1 Hz,1H), 6.46 (d, J=16.2 Hz, 1H), 4.37-4.51 (m, 4H), 2.97-3.10 (m, 4H).

¹³C-NMR (CDCl₃, 100 MHz): 166.5 (s), 153.2 (s), 149.5 (s), 137.9 (s),137.8 (s), 136.8 (d), 131.1 (d), 129.7 (d), 129.0 (d), 128.9 (d), 128.9(d), 128.6 (d), 128.6 (d), 128.5 (d), 127.8 (d), 127.8 (d), 127.0 (s),126.8 (d), 126.6 (d), 126.5 (d), 122.6 (d), 120.5 (d), 69.4 (t), 65.1(t), 35.2 (t), 35.0 (t).

MS (EI, 70 eV): 417 (<1, [M+1 ]⁺), 370 (4), 164 (8), 146 (7), 105 (100),104 (31).

EXAMPLE 10 3-[2-(3-Methyl-5-phenyl-pentyloxycarbonyloxy)-phenyl]-acrylicacid phen-ethyl ester

Following the general procedure described in Example 9 the titlecompound is prepared, using 3-(2-hydroxy-phenyl)-acrylic acid phenethylester (1.61 g, 6.0 mmol), chloroformic acid 3-methyl-5-phenyl-pentylester (1.59 g, 6.6 mmol, 1.1 equiv.) and pyridine (0.97 ml, 12.0 mmol,2.0 equiv.).3-[2-(3-Methyl-5-phenyl-pentyloxycarbonyloxy)-phenyl]-acrylic acidphenethyl ester (1.65 g, 58% yield) is obtained as colourless, viscousoil.

IR (film):1760 s, 1712 s, 1251 s, 1211 vs, 1167 vs, 697 vs.

¹H-NMR (CDCl₃, 400 MHz): 7.82 (d, J=16.2 Hz, 1H), 7.61 (dd, J=7.8, 1.6Hz, 1H), 7.37-7.44 (m, 1H), 7.13-7.35 (m, 13H), 6.46 (d, J=16.2 Hz, 1H),4.41 (t, J=7.1 Hz, 2H), 4.25-4.37 (m, 2H), 3.00 (t, J=7.1 Hz, 2H),1.79-1.94 (m, 1H), 1.46-1.76 (m, 5H), 1.02 (d, J=6.3 Hz, 3H)

¹³C-NMR (CDCl₃, 100 MHz): 166.5 (s), 153.3 (s), 149.5 (s), 142.5 (s),137.9 (d), 137.8 (s), 131.1 (d), 128.9 (d), 128.5 (d), 128.3 (d), 128.3(d), 127.9 (d), 127.0 (s), 126.6 (d), 126.5 (d), 125.7 (d), 122.6 (d),120.5 (d), 67.7 (t), 65.1 (t), 38.8 (t), 35.3 (t), 35.2 (t), 33.2 (t),29.4 (d), 19.4 (q).

MS (EI, 70 eV): 472 (<1, M⁺), 426 (4), 313 (5), 164 (34), 160 (39), 146(32), 105 (91), 91 (100).

EXAMPLE 11-15

Further compounds as listed in Table 1 were prepared according to thegeneral procedure described in the specification.

TABLE 1 IR (film) MS (EI 70 ev) NMR (¹H NMR (400 MHz, CDCl₃) δ in ppm)Benzoic acid4-benzoylamino-2-[2-(3,7-dimethyl-oct-6-enyloxycarbonyl)vinyl]phenylester (11) 1713s, 527 ([M + 2]⁺), 0.87 (m, 3H), 1.15 (m, 1H), 1.31 (m,2H), 1.44 (m, 2H), 1654s, 388 (26), 1.52 (m, 2H), 1.59 (s, 3H), 1.66 (s,3H), 1.94 (m, 2H), 4.17 (m, 1525s, 371 (24), 265 (33), 2H), 5.08 (m,1H), 6.52 (d, J = 16, 1H), 7.25 (d, J = 9, 1H), 1196vs, 105 (100). 7.55(m, 5H), 7.66 (m, 2H), 7.80, (d, J = 16, 1H), 7.90 (m, 2H), 704vs. 8.13(d, J = 3, 1H), 8.23 (dd, J = 8, 1, 2H).3-(2-Acetoxy-5-tert-butyl-phenyl)acrylic acid 3,7-dimethyl-oct-6-enylester (12) 1768m, 400 (2, M⁺), 0.94 (d, J = 7, 3H), 1.18-1.80 (series ofm, 5H), 1.33 (s, 9H), 1713s, 262 (29, 220 1.61 (s, 3H), 1.68 (s, 3H),2.0 (m, 2H), 2.36 (s, 3H), 4.25 (m, 1182vs. (28), 202 (66), 2H), 5.10(m, 1H), 6.45 (d, J = 16, 1H), 7.04 (d, J = 9, 1H), 187 (100), 7.42 (dd,J = 9, 2, 1H), 7.62 (d, J = 2, 1H), 7.74 (d, J = 16, 1H). 159 (30).3-(2-Acetoxy-phenyl)acrylic acid 3,7-dimethyl-oct-6-enyl ester (13)1770m, 344 (<1, M⁺), 0.95 (d, J = 7, 3H), 1.23 (ddd, J = 9, 7, 6, 1H),1.37 (m, 1H), 1713s, 147 (92), 1.51 (m, 1H), 1.61 (s, 3H), 1.58-1.80 (m,2H), 1.68 (s, 3H), 1637w, 138 (68), 95 (76), 2.01 (m, 2H), 2.37 (s, 3H),4.24 (m, 2H), 5.10 (ddd, J = 7, 6, 1174vs. 81 (100). 1, 1H), 6.45 (d, J= 16, 1H), 7.12 (dd, J = 8, 1, 1H), 7.26 (m, 1H), 7.40 (td, J = 8, 2,1H), 7.64 (dd, J = 8, 2, 1H), 7.74 (d, J = 16, 1H).3-(2-Ethoxycarbonyloxy-phenyl)acrylic acid dec-9-enyl ester (14) 1763s,374 (4, M⁺), 1.37 (m, 13H), 1.69 (qd, J = 7, 7, 2H), 2.04 (q, J = 7,2H), 1714s, 285 (4), 4.19 (t, J = 7, 2H), 4.33 (q, J = 7, 2H), 4.93 (d,J = 10, 1H), 1638m, 192 (3), 164 (7), 4.99 (dd, J = 17, 2, 1H), 5.81 (m,1H), 6.48 (d, J = 16, 1H), 1249s, 146 (100), 7.25 (m, 2H), 7.40 (m, 1H),7.63 (d, J = 8, 1H), 7.82 (d, 1212vs, 118 (34). J = 16, 1H). 1170vs3-(2-{2-[2-(3,7-Dimethyl-oct-6-enyloxycarbonyl)vinyl]phenoxycarbonyloxy}phenyl)-acrylic acid 3,7-dimethyl-oct-6-enyl ester (15) 1784w, 630 (4, M⁺), 0.95(d, J = 6, 6H), 1.18-1.80 (series of m, 10H), 1.57 (s, 6H), 1712s, 493(12), 1.67 (d, J = 1, 6H), 1.99 (m, 4H), 4.26 (m, 4H), 1638w, 475 (100),5.08 (m, 2H), 6.53 (d, J = 16, 2H), 7.31 (m, 4H), 7.44 (m, 2H), 1165vs.431 (15), 337 (65), 7.65 (dd, J = 8, 2, 2H), 7.90 (d, J = 16, 2H). 249(60), 147 (60).

EXAMPLE 16 3-(2-Hydroxy-4-methoxy-phenyl)-acrylic acid3,7-dimethyl-oct-6-enyl ester

The compound is prepared by reaction of 7-methoxycoumarin withcitronellol in the presence of sodium hydride following the proceduredescribed in Example 2. The title compound is isolated as a viscous,colourless oil.

IR (film):3331 br., 1705 s, 1676 s, 1611 vs, 1518 m, 1169 vs, 836 w, 802w.

¹H-NMR (CDCl₃, 400 MHz): 7.98 (d, J=16.2 Hz, 1H), 7.30-7.39 (m, 2H),6.34-6.63 (m, 3H), 5.03-5.20 (m, 1H), 4.18-4.37 (m, 2H), 3.79 (s, 3H),2.06 (m, 2H), 1.10-1.87 (m, 5H), 1.68 (s, 3H), 1.61 (s, 3H), 0.95 (d,J=6.6 Hz, 3H).

MS (EI, 70 eV): 348 (<1, M⁺), 194 (81), 177 (87), 176 (100), 148 (54),133 (39).

EXAMPLE 17 3-(2-Hydroxy-5-methyl-phenyl)-acrylic acid2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-but-2-enyl ester

The compound is prepared by reaction of 6-methylcoumarin with2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-but-2-en-1-ol in thepresence of sodium hydride following the procedure described in Example2. The compound is isolated as a viscous, slightly yellow oil.

IR (film):3313 s, 3035m, 2958 vs, 1688 s, 1627 s, 1508 m, 1463 s, 1155s, 816 m, 799 m.

¹H-NMR (CDCl₃, 200 MHz 8.00 (d, J=16.2 Hz, 1H), 7.17-7.36 (m, 1H),6.92-7.13 (m, 2H), 6.74 (d, J=8.2 Hz, 1H), 6.61 (d, J=16.2 Hz, 1H),5.31-5.63 (m, 2H), 5.22 (s, 2H), 4.66 (s, 1H), 4.07 (s, 2H), 2.26 (s,3H), 1.67-2.45 (m, 4H), 1.62-1.56 (m, 3H), 0.90 (t, J=7.6 Hz, 3H), 0.89(s, 3H), 0.78 (s, 3H).

MS (EI, 70 eV): 368 (<1, M⁺), 190 (17), 161 (53), 108 (100).

EXAMPLE 18 3-(2-Hydroxy-4-methoxy-phenyl)-acrylic acid3-methyl-5-phenyl-pentyl ester

The compound is prepared by reaction of 7-methoxycoumarin withcitronellol in the presence of sodium hydride following the proceduredescribed in Example 2. The compound is isolated as a white solid, m.p.70-73° C.

IR (film):1760 s, 1712 s, 1251 s, 1211 vs, 1167 vs, 697 vs.

¹H-NMR (CDCl₃, 400 MHz): 8.00 (d, 4=15.9 Hz, 1H), 7.93 (br. s, 1H),7.11-7.39 (m, 6H), 6.55 (d, J=15.9 Hz, 1H), 6.42-6.49 (m, 2H), 4.19-4.34(m, 2H), 3.74 (s, 3H), 2.52-2.74 (m, 2H), 1.41-1.89 (m, 5H), 1.00 (d,J=6.3 Hz, 3H).

¹³C-NMR (CDCl₃, 100 MHz): 169.4 (s), 162.5 (s), 157.5 (s), 142.6 (s),141.1 (s), 130.5 (s), 128.3 (d), 125.6 (d), 115.0 (s), 114.9 (d), 106.8(d), 101.7 (d), 63.0 (t), 55.3 (q), 38.7 (t), 35.4 (t), 33.2 (t), 29.5(d), 19.4 (q).

MS (EI, 70 eV). 354 (30, M⁺), 194 (78), 176 (100), 148 (46), 133 (17),104 (14), 91 (40).

EXAMPLES 19

The compounds of Example 16, 17 and 18 may be used as intermediates forthe preparation of further compounds A, B and C according to the presentinvention. Their preparation may be carried with the correspondingchloroformates following the general procedure of Example 9.

3-[2-(3,7-Dimethyl-oct-6-enyloxycarbonyloxy)-4-methoxy-phenyl]-acrylicacid 3,7-dimethyl-oct-6-enyl ester

3-(2-Benzyloxycarbonyloxy-5-methyl-phenyl)-acrylic acid2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-but-2-enylester

3-[2-(4-tert-Butyl-cyclohexyloxycarbonyloxy)-4-methoxy-phenyl]-acrylicacid 3-methyl-5-phenyl-pentyl ester

EXAMPLE 20 UV-Spectra Comparison (Protected/Non Protected Fragrance inPresence of a Fabric Conditioner)

Solutions A to D, 5 ml each, were prepared using CH₃CN/H₂O (3:2) as asolvent and their colour visually judged.

Fragrance Precursor Additive Solution (each added at 0.1 mg/ml) (amount)Colour A (E)-3-(2-Hydroxy-phenyl)acrylic acid none colourless dec-9-enylester (Ex. 2) B As above (A) Fabric Bright conditioner¹⁾ yellow (30 mg)C 3-{2-[2-(2-Dec-9-enyloxycarbonyl- none colourlessvinyl)phenoxycarbonyloxy]-phenyl}- acrylic acid dec-9-enyl ester (Ex. 3)D As above (C) Fabric colourless conditioner¹⁾ (30 mg) ¹⁾Aqueous fabricconditioner emulsion containing 12.7% wt/wt of active cationicsurfactant

After adding a fabric conditioner to a solution comprising anunprotected fragrance precursor (solution A/B) the solution turnedbright yellow, whereas a solution comprising a protected fragranceprecursor (solution C/D) remains colourless.

The UV-spectra of solutions A to D were recorded and are depicted inFIG. 1. They show that upon addition of the fabric conditioner thehighest λ_(max) at 326 nm (UV) shifts to 394 nm (visible light), whereasthe highest π_(max) of the protected fragrance precursor remainsunchanged at 270 nm upon addition of the fabric conditioner.

EXAMPLE 21 Application in Fabric Conditioner

The deposition and cleavage of the compounds of formula (I) on cotton(white towels) in a typical wash/rinse cycle is determined as describedin the following. All handling of samples containing a compound offormula (I) is done with as little exposure to light as possible.

An aqueous fabric conditioner emulsion containing 12.7% wt/wt of activecationic surfactant and 0.5% wt/wt of a compound of formula (I) isprepared. Whereas samples with free o-coumarates turn yellow, sampleswith protected o-coumarates remain white. A wash/rinse cycle (40° C.program) in a standard washing machine is performed with a 1 kg washload consisting of 25 cotton terry towels, adding the following:

-   -   1) 62 g of a standard concentrated unperfumed washing powder        containing protease, cellulase, and lipase for the washing cycle    -   2) 16 g of fabric conditioner as prepared above for the rinse        cycle (containing 80 mg of a compound of formula (I) as        indicated in Table 2, compound Ex. No 6, 5, 3, 4 or 14, or a        compound of formula (A), i.e. comp. Ex. No. 1 or 2, as        comparison as indicated in Table 2.

The towels are removed from the washing machine and dried in the darkfor 24 h at room temperature and 40% relative humidity. Three towels(representing each 4% of the total wash load) are removed and placedindividually in a Soxhlet apparatus containing 0.5 l of methylenechloride and extracted for 5 h. The solvent is removed carefully in arotary evaporator and the residues are standardized to 10 mlacetonitrile solution. These solutions are analyzed by RP-HPLC using aH₂O/acetonitrile gradient and UV-detection at 258 nm. The concentrationsof “protected” and “unprotected” fragrance precursor per sample aredetermined via external calibration and a mean value is calculated fromthe three towels. From this, the mean deposition rate in % of theorycompared to the molar amount of protected precursor applied via thefabric conditioner for the two precursor types is calculated. Theresults are listed in Table 2.

Best cleavage rate by lipase is observed for carbonates derived fromshort chain primary alcohols (Comp. Ex. No. 6) and (Comp. Ex. No 14).The best combined deposition/cleavage result is obtained from thesymmetrical carbonate (Comp. Ex. No. 3). The final deposition of freeprecursor using this compound is higher than by administration of thecorresponding “unprotected” 3-(2-Hydroxy-phenyl)-acrylic acid ester(Comp. Ex. No. 2).

As used herein “unprotected fragrance precursor” means a compoundcomprising a hydroxyl group, i.e. the prior art compound (A), and“protected fragrance precursor” means a compound of formula (I)according to the present invention.

TABLE 2 Releases Modified Comp. Protecting Coumarin Prec. Free prec.Cleavage Ex. N^(o) Fragrance precursor group and [Depos. %] [Depos. %][%] 1 3-(2-Hydroxy-phenyl)acrylic acid 3,7- None Citronellol — 45 —dimethyl-oct-6-enyl ester 2 3-(2-Hydroxy-phenyl)acrylic acid dec-9- None9-Decen-1-ol — 46 — enyl ester 6 3-(2-Hex-3-enyloxycarbonyloxy-cis-3-hex. carbonate Citronellol & 2 50 97 phenyl)acrylic acid3,7-dimethyl-oct-6- cis-3-hexenol 5 3-[2-(3,7-Dimethyl-oct-6-Citronellylcarbonate Citronellol 69 11 14enyloxycarbonyloxy)-phenyl]acrylic acid 3,7-dimethyl-oct-6-enyl ester 33-{2-[2-(2-Dec-9-enyloxycarbonyl- Sym. Carbonate 9-Decen-1-ol 34 66 66vinyl)phenoxycarbonyloxy]phenyl}- acrylic acid dec-9-enyl ester 43-(2-Dec-9-enyloxycarbonyloxy- Rosalva-Carbonate 9-Decen-1-ol 32 34 68phenyl)acrylic acid dec-9-enyl ester 143-(2-Ethoxycarbonyloxy-phenyl)acrylic Ethylcarbonate 9-Decen-1-ol 5 4291 acid dec-9-enyl ester

1. A process for preparing compositions which provide upon activation anolfactory compound comprising incorporating into the composition acompound of formula (I) as precursor for olfactory compounds compound

wherein the acrylic acid ester double bound is of the E configuration; nis zero or 1; Y is —CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue, and the sum of all carbonatoms (R⁵+R⁶+R⁷) is not greater than 18; or Y is —CR⁵R⁶R⁷, wherein R⁵,R⁶ and R⁷ are independently hydrogen or a C₁-C₁₈ hydrocarbon residuecontaining one or more atoms/groups selected from O, N and C(O), and thesum of all carbon atoms (R⁵+R⁶+R⁷) is not greater than 18; or Y is—CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈ hydrocarbon residue, the geometry of the enol double bond is E orZ, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰) is not greater than 18;or Y is CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen ora C₁-C₁₈ hydrocarbon residue containing one or more atoms/groupsselected from O, N and C(O), the geometry of the enol double bond is Eor Z, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰) is not greater than18; R² and R³ are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxyresidue, —NH₂, —NO₂, —NHCO₂CH₃, —N(C₁-C₆ alkyl)₂, —N(hydroxyalkyl)₂,—NHC(O)—(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl); or R² and R³ are attachedat the positions C(6,7), C(7,8), or C(8,9), and form together with thecarbon atoms to which they are attached a dioxolane ring or a dioxanering; R⁴ in 2- or 3-position is hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₃-C₆ cycloalkyl, or —CN; and a) if n is zero, R is a C₁-C₂₄ hydrocarbonresidue, or C₁-C₂₄ hydrocarbon residue containing one or moreheteroatoms selected from N, O and Si; or b) if n is 1, R is a C₁-C₂₅hydrocarbon residue, a C₁-C₂₋₅ hydrocarbon residue containing one ormore atoms/groups selected from N, O, Si, and C(O), or C₁-C₂₅hydrocarbon residue substituted by an ionic substituent of the formulaN(R²⁰)₃ ⁺, in which R²⁰ is the residue of an alkyl group with 1 to 18carbon atoms; or R is a monovalent residue of the formula (I)

wherein X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁶ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue, and the sum of all carbonatoms (R¹⁴+R¹⁵+R¹⁶) is not greater than 18; or X is —CR¹⁴R¹⁵R¹⁶, whereinR¹⁴, R¹⁵ and R¹⁶ are independently hydrogen or a C₁-C₁₈ hydrocarbonresidue containing one or more atoms/groups selected from O, N and C(O),and the sum of all carbon atoms (R¹⁴+R¹⁵+R¹⁶) is not greater than 18; orX is CR¹⁷=CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently hydrogenor a C₁-C₁₈ hydrocarbon residue, the geometry of the enol double bond isE or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not greaterthan 18; or X is —CR¹⁷═CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ areindependently hydrogen or a C₁-C₁₈ hydrocarbon residue containing one ormore atoms/groups selected from O, N and C(O), the geometry of the enoldouble bond is E or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) isnot greater than 18; R¹² and R¹³ are independently hydrogen, C₁-C₆alkyl, C₁-C₆ alkoxy residue, —NO₂, —NH₂, —NHCO₂CH₃, —N(C₁-C₆ alkyl)₂,—N(hydroxyalkyl)₂, —NHC(O)—(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl); or R¹²and R¹³ are attached at the positions C(vi,vii), C(vii,viii), orC(viii,ix), and form together with the carbon atoms to which they areattached a dioxolane ring or a dioxane ring; R¹¹ in ii- or iii-positionis hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₃-C₆ cycloalkyl, or —CN. 2.(canceled)
 3. (canceled)
 4. (canceled)
 5. (canceled)
 6. A processaccording to claim 1 for preparing compositions which provide uponactivation an olfactory compound comprising incorporating into thecomposition a compound of formula (I) wherein R⁵, R⁶ and R⁷ areindependently hydrogen or a C₁-C₁₀ hydrocarbon residue.
 7. A processaccording to claim 1 wherein the sum of carbon atoms R⁵+R⁶+R⁷ is between6 and
 15. 8. A process according to claim 1 for preparing compositionswhich provide upon activation an olfactory compound comprisingincorporating into the composition a compound of formula (I) wherein atleast one residue R⁵, R⁶ and R⁷ is not hydrogen.
 9. A process accordingto claim 1 for preparing compositions which provide upon activation anolfactory compound comprising incorporating into the composition acompound of formula (I) wherein R⁸, R⁹ and R¹⁰ are independentlyhydrogen or a C₁-C₁₀ hydrocarbon residue.
 10. A process according toclaim 1 wherein the sum of carbon atoms R⁵+R⁹+R¹⁰ is between 6 and 15.11. A process according to claim 1 for preparing compositions whichprovide upon activation an olfactory compound comprising incorporatinginto the composition a compound of formula (I) wherein at least oneresidue R⁸, R⁹ and R¹⁰ is not hydrogen.
 12. A process according to claim1 for preparing compositions which provide upon activation an olfactorycompound comprising incorporating into the composition a compound offormula (I) wherein R¹⁴, R¹⁵ and R¹⁶ are independently hydrogen or aC₁-C₁₀ hydrocarbon residue.
 13. A process according to claim 1 whereinthe sum of carbon atoms R¹⁴+R¹⁵+R¹⁶ is between 6 and
 15. 14. A processaccording to claim 1 for preparing compositions which provide uponactivation an olfactory compound comprising incorporating into thecomposition a compound of formula (I) wherein at least one residue R¹⁴,R¹⁵ and R¹⁶ is not hydrogen.
 15. A process according to claim 1 forpreparing compositions which provide upon activation an olfactorycompound comprising incorporating into the composition a compound offormula (I) wherein R¹⁷, R¹⁸ and R¹⁹ are independently hydrogen or aC₁-C₁₀ hydrocarbon residue.
 16. A process according to claim 1 whereinthe sum of carbon atoms R¹⁷+R¹⁸+R¹⁹ is between 6 and
 15. 17. A processaccording to claim 1 for preparing compositions which provide uponactivation an olfactory compound comprising incorporating into thecomposition a compound of formula (I) wherein at least one residue R¹⁷,R¹⁸ and R¹⁹ is not hydrogen.
 18. A process according to claim 1 forpreparing compositions which provide upon activation an olfactorycompound comprising incorporating into the composition a compound offormula (I) wherein n is
 1. 19. A process according to claim 1 forpreparing compositions which provide upon activation an olfactorycompound comprising incorporating into the composition a compound offormula (I) wherein n is 1 and Y a residue selected from the groupconsisting of a fragrant alcohol HO—CR⁵R⁶R⁷, of the enol form of afragrant aldehyde of the formula O═(CH)—CHR⁹R¹⁰, and of the enol form ofa fragrant ketone of the formula O═(CR⁸)—CHR⁹R¹⁰.
 20. A processaccording to claim 19 wherein the fragrant alcohol having a molecularweight between 46 and
 400. 21. A process according to claim 1 forpreparing compositions which provide upon activation an olfactorycompound comprising incorporating into the composition a compound offormula (I) wherein n is 1 and Y a residue selected from the groupconsisting of a fragrant alcohol HO—CR⁵R⁶R⁷, of the enol form of afragrant aldehyde of the formula O═(CH)—CHR⁹R¹⁰, and of the enol form ofa fragrant ketone of the formula O═(CR⁸)—CHR⁹R¹⁰, and R is selected fromthe group consisting of methyl, ethyl, propyl, butyl, pentyl,2-ethylhexyl, cyclopentyl, cyclohexyl, and the residue of a fragrantalcohol.
 22. A process according to claim 21 wherein the fragrantalcohol having a molecular weight between 46 and
 400. 23. A processaccording to claim 19 wherein the fragrant aldehyde having a molecularweight between 100 and
 450. 24. A process according to claim 21 whereinthe fragrant aldehyde having a molecular weight between 100 and
 450. 25.A process according to claim 19 wherein the fragrant ketone having amolecular weight between 100 and
 450. 26. A process according to claim21 wherein the fragrant ketone having a molecular weight between 100 and450.
 27. A process according to claim 1 for preparing compositions whichprovide upon activation an olfactory compound comprising incorporatinginto the composition a compound of formula (I) wherein n is 1 and R isamonovalent residue of formula (i).
 28. A consumer product comprising acompound of formula (I) as defined by claim
 1. 29. A consumer productaccording to claim 28 comprising a compound of formula (I) wherein n is1 and Y a residue selected from the group consisting of a fragrantalcohol HO—CR⁵R⁶R⁷, of the enol form of a fragrant aldehyde of theformula O═(CH)—CHR⁹R¹⁰, and of the enol form of a fragrant ketone of theformula O═(CR⁸)-CHR⁹R¹⁰.
 30. A consumer product according to claim 28wherein the consumer product is selected from fine fragrance, industrialcare products, institutional care products, home care products, personalcare products, industrial cleaning products, institutional cleaningproducts, home cleaning products, and fabric conditioner.
 31. A processof providing an olfactory compound to a substrate comprising the steps:a) cleaving a compound of formula (I) by hydrolysis

wherein the acrylic acid ester double bound is of the E configuration; nis zero or 1; Y is —CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue, and the sum of all carbonatoms (R⁵+R⁶+R⁷) is not greater than 18; or Y is —CR⁵R⁶R⁷, wherein R⁵,R⁶ and R⁷ are independently hydrogen or a C₁-C₁₈ hydrocarbon residuecontaining one or more atoms/groups selected from O, N and C(O), and thesum of all carbon atoms (R⁵+R⁶+R⁷) is not greater than 18; or Y is—CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈ hydrocarbon residue, the geometry of the enol double bond is E orZ, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰) is not greater than 18;or Y is —R⁸═CR⁹R¹⁰, wherein 18, 19 and R¹⁰ are independently hydrogen ora C₁-C₁₈ hydrocarbon residue containing one or more atoms/groupsselected from O, N and C(O), the geometry of the enol double bond is Eor Z, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰) is not greater than18; R² and R³ are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxyresidue, —NH₂, —NO₂, —NHCO₂CH₃, —N(C₁-C₆ alkyl)₂, —N(hydroxyalkyl)₂,—NHC(O)-(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl); or R² and 13 are attachedat the positions C(6,7), C(7,8), or C(8,9), and form together with thecarbon atoms to which they are attached a dioxolane ring or a dioxanering; R⁴ in 2- or 3-position is hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₃-C₆ cycloalkyl, or CN; and a) if n is zero, R is a C₁-C₂₄ hydrocarbonresidue, or C₁-C₂₋₄ hydrocarbon residue containing one or moreheteroatoms selected from N, O and Si; or b) if n is 1, R is a C₁-C₂₅hydrocarbon residue, a C₁-C₂₅ hydrocarbon residue containing one or moreatoms/groups selected from N, O, Si, and C(O), or C₁-C₂₅ hydrocarbonresidue substituted by an ionic substituent of the formula N(R²⁰)₃ ⁺, inwhich R²⁰ is the residue of an alkyl group with 1 to 18 carbon atoms; orR is a monovalent residue of the formula (I)

wherein X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁶ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue, and the sum of all carbonatoms (R¹⁴+R¹⁵+R¹⁶) is not greater than 18; or X is —CR¹⁴R¹⁵R¹⁶, whereinR⁴, R¹⁵ and R⁶ are independently hydrogen or a C₁-C₁₈ hydrocarbonresidue containing one or more atoms/groups selected from O, N and C(O),and the sum of all carbon atoms (R¹⁴+R¹⁵+R¹⁶) is not greater than 18; orX is CR⁷═CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently hydrogen ora C₁-C₁₈ hydrocarbon residue, the geometry of the enol double bond is Eor Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not greater than18; or X is —CR¹⁷=CR⁸R⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue containing one or moreatoms/groups selected from O, N and C(O), the geometry of the enoldouble bond is E or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) isnot greater than 18; R¹² and R¹³ are independently hydrogen, C₁-C₆alkyl, C₁-C₆ alkoxy residue, —NO₂, —NH₂, —NHCO₂CH₃, —N(C₁-C₆ alkyl)₂,—N(hydroxyalkyl)₂, —NHC(O)—(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl); or R¹²and R¹³ are attached at the positions C(vi,vii), C(vii,viii), orC(viii,ix), and form together with the carbon atoms to which they areattached a dioxolane ring or a dioxane ring; R¹¹ in ii- or iii-positionis hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₃-C₆ cycloalkyl, or —CN;resulting in a compound of formula (Ia)

wherein R², R³, R⁴ and Y have the same meaning as given above; followedby b) cleaving the compound of formula (Ia) of step a under activatingconditions in the presence of light resulting in a coumarin (IIa)

wherein R², R³ and R⁴ have the same meaning as given above.
 32. Acompound of formula (I)

wherein the acrylic acid ester double bound is of the E configuration; nis zero or 1; Y is CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue, and the sum of all carbonatoms (R⁵+R⁶+R⁷) is not greater than 18 and at least 6; or Y is—CR⁵R⁶R⁷, wherein R⁵, R⁶ and R⁷ are independently hydrogen or a C₁-C₁₁aliphatic residue containing one or more atoms/groups selected from O, Nand C(O), the sum of all carbon atoms (R⁵+R⁶+R⁷) is not greater than 18;and at least one of the residues R⁵, R⁶ and R⁷ is not hydrogen; or Y is—CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogen or aC₁-C₁₈ hydrocarbon residue, the geometry of the enol double bond is E orZ, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰) is not greater than 18;or Y is —CR⁸═CR⁹R¹⁰, wherein R⁸, R⁹ and R¹⁰ are independently hydrogenor a C₁-C₁₈ hydrocarbon residue containing one or more atoms/groupsselected from O, N and C(O), the geometry of the enol double bond is Eor Z, and the sum of all carbon atoms (R⁸+R⁹+R¹⁰) is not greater than18; R² and R³ are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxyresidue, —NH₂, —NO₂₁—NHCO₂CH₃, —N(C₁-C₆ alkyl)₂, —N(hydroxyalkyl)₂,—NHC(O)—(C₁-C₈ alkyl) or —NHC(O)—(C₃-C₈ aryl); or R² and R³ are attachedat the positions C(6,7), C(7,8), or C(8,9), and form together with thecarbon atoms to which they are attached a dioxolane ring or a dioxanering; R⁴ in 2- or 3-position is hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₃-C₆ cycloalkyl, or —CN; and a) if n is zero, R is a C₂-C₂₄ hydrocarbonresidue, or C₁-C₂₄ hydrocarbon residue containing one or moreheteroatoms selected from N, O and Si; or b) if n is 1, R is a C₁-C₂₅hydrocarbon residue, a C₁-C₂₅ hydrocarbon residue containing one or moreatoms/groups selected from N, O, Si, and C(O), or C₁-C₂₅ hydrocarbonresidue substituted by an ionic substituent of the formula N(R²⁰)₃ ⁺, inwhich R²⁰ is the residue of an alkyl group with 1 to 18 carbon atoms; orR is a monovalent residue of the formula (I)

wherein X is —CR¹⁴R¹⁵R¹⁶, wherein R¹⁴, R¹⁵ and R¹⁶ are independentlyhydrogen or a C₁-C₁₈ hydrocarbon residue, and the sum of all carbonatoms (R¹⁴+R¹⁵+R¹⁶) is not greater than 18; or X is —CR¹⁴R¹⁵R¹⁶, whereinR¹⁴, R¹⁵ and R¹⁶ are independently hydrogen or a C₁-C₁₈ hydrocarbonresidue containing one or more atoms/groups selected from O, N and C(O),and the sum of all carbon atoms (R¹⁴+R¹⁵+R¹⁶) is not greater than 18; orX is —CR¹⁷═CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ are independently hydrogenor a C₁-C₁₈ hydrocarbon residue, the geometry of the enol double bond isE or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) is not greaterthan 18; or X is —CR¹⁷=CR¹⁸R¹⁹, wherein R¹⁷, R¹⁸ and R¹⁹ areindependently hydrogen or a C₁-C₁₈ hydrocarbon residue containing one ormore atoms/groups selected from O, N and C(O), the geometry of the enoldouble bond is E or Z, and the sum of all carbon atoms (R¹⁷+R¹⁸+R¹⁹) isnot greater than 18; R¹² and R¹³ are independently hydrogen, C₁-C₆alkyl, C₁-C₆ alkoxy residue, —NO₂, —NH₂, —NHCO₂CH₃, —N(C₁-C₆ alkyl)₂,—N(hydroxyalkyl)₂, —NHC(O)—(C₁-C₉ alkyl) or —NHC(O)—(C₃-C₈ aryl); or R¹²and R¹³ are attached at the positions C(vi,vii), C(vii,viii), orC(viii,ix), and form together with the carbon atoms to which they areattached a dioxolane ring or a dioxane ring; R¹¹ in ii- or iii-positionis hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₃-C₆ cycloalkyl, or —CN.
 33. Acompound according to claim 32 wherein n is 1 and R², R³ and R⁴ arehydrogen.
 34. A compound according to claim 32 wherein n is 1, R² and R³are hydrogen and R⁴ is selected from methyl and —CN.
 35. A compoundaccording to claim 32 wherein n is 1, R² and R³ are hydrogen and R⁴ isphenyl at C(3).
 36. A compound according to claim 32 wherein n is 1, 2is hydrogen, R³ is at either C(6) to C(8) and R³ is selected frommethyl, ethyl, propyl, isopropyl, methoxy, ethoxy and propyloxy, and R⁴is selected from hydrogen, methyl, —CN, and phenyl at C(3).
 37. Acompound according to claim 32 wherein n is 1, R² and R³ are methyl atposition C(6,7), C(6,8), C(6,9), C(7,8), or C(9,9), and R⁴ is selectedfrom hydrogen, —CN, and phenyl at C(3).
 38. A compound according toclaim 32 wherein n is 1, R² and R³ are methoxy at C(7,9), and R⁴ isselected from hydrogen, —CN, and phenyl at C(3).
 39. A compoundaccording to claim 32 wherein n is 1, R⁴ is selected from hydrogen,methyl, —CN, and phenyl at C(3), R² is methyl at C(6) and R³ isisopropyl at C(9).
 40. A compound according to claim 32 wherein n is 1,R⁴ is selected from hydrogen, methyl, —CN, and phenyl at C(3), R² isisopropyl at C(6) and R³ is methyl at C(9).
 41. A compound according toclaim 32 wherein n is 1, R⁴ is selected from hydrogen and methyl, and R²and R³ are hydrogen.
 42. A compound according to claim 32 wherein n is1, R⁴ is selected from hydrogen and methyl, R² is hydrogen, and R³ is7-methoxy.
 43. A compound according to claim 32 wherein n is 1, R⁴ isselected from hydrogen and methyl, R² is hydrogen, and R³ is 6-methyl.44. A compound according to claim 32 wherein n is 1, R⁴ is selected fromhydrogen and methyl, R² is hydrogen, and R³ is 7-methyl.
 45. A compoundaccording to claim 32 wherein n is 1, R⁴ is selected from hydrogen andmethyl, R² is hydrogen, and R³ is 8-methyl.
 46. A compound according toclaim 32 wherein n is 1, R⁴ is selected from hydrogen and methyl, R² ishydrogen, and R³ is 6-tert-butyl.
 47. A compound according to claim 32wherein n is 1, R⁴ is selected from hydrogen and methyl, R² is6-tert-butyl, and R³ is 8-tert-butyl.
 48. A compound according to claim32 wherein n is 1 and R is a monovalent residue of the formula (I)

wherein X, R¹¹, R¹² and R¹³ are defined according to claim
 27. 49. Acompound according to claim 48 wherein R⁴═R¹¹, R³═R¹³ and R²═R¹².
 50. Aprocess according to claim 31 wherein the compound of formula (I)hydrolysis in the presence of enzymes.